Haloalkyl hydroxy-aromatic condensation products as lubricant additives

ABSTRACT

Condensation products made by reacting an alphahaloalkyl hydroxy-aromatic compound also having at least one non-fused hydrocarbyl substituent with at least one olefinic nitrile, carboxylic acid or carboxylic acid derivative are useful as additives for fuels and lubricants. The number of carbon atoms in the aromatic hydrocarbyl compound&#39;s substituents are each about 25 while the haloalkyl group contains from one to about 36 carbons. The acid or nitrile reactant usually contains three to about forty carbons. Products made from halomethyl alkyl-substituted phenols and α,β-olefinic diacid derivatives such as maleic anhydride are particularly useful. Similarly useful products can be made from these condensation products by further reacting their acid, acid derivative or nitrile groups with alcohols, polyols, monoamines, polyamines, metal salts or metals.

REFERENCE TO RELATED APPLICATIONS

This application is a division of my co-pending U.S. application Ser.No. 684,818 filed May 10, 1976 now U.S. Pat. No. 4,108,783, which is acontinuation-in-part of my then co-pending application Ser. No. 459,424filed Apr. 9, 1974.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to novel condensation products useful asadditives for lubricants and normally liquid fuels, as well as tolubricant and normally liquid fuel compositions containing theseadditives. It also relates to processes for making such products andconcentrates containing them. More particularly the additives of thisinvention are made by reacting certain alpha-haloalkyl hydroxy-aromaticcompounds with an olefinic nitrile, acid or acid derivative.

2. Description of the Prior Art

The use of relatively high molecular weight compositions characterizedby the presence within their structure of both lipophilic and lipophobicgroups as additives for normally liquid fuels (e.g., gasoline, jet fuel,kerosene, fuel oil, heating oil, etc.) and naturally occurring andsynthetic lubricants, is well known to the art. See, for example, thediscussions in "Lubricant Additives" by C. V. Smalheer and R. KennedySmith published by the Lezius-Hiles Co., Cleveland, Ohio, particularlypages 2-5, and "Lubricant Additives" by M. W. Ranney, published by theNoyes Data Corporation, Park Ridge, New Jersey (1973), particularlypages 3-92.

Among the additives that have been used in fuel and lubricants are thosedescribed in U.S. Pat. Nos. 3,701,640; 3,558,743; and 3,493,520.

The materials described in U.S. Pat. No. 3,558,743 and U.S. Pat. No.3,493,520 patents are made by reacting a carboxylic acid- oranhydride-containing addition copolymer, an amine, an alkylated phenoland an aldehyde, while those described in U.S. Pat. No. 3,701,640 patentare made by reacting a carboxylic acid with a polyamine having at leastthree nitrogen atoms, at least two of which are primary and at least onewhich is secondary, and alkyl-substituted phenol and formaldehyde.Trimerization of chloromethyl phenols has been reported in Journal ofthe Chemical Society, Perkin I, 359 (1973). This reaction is believed tooccur through quinone methides such as those described by A. B. Turner,"Quarterly Reviews", 18, 347 (1964).

Despite the knowledge evidenced by the above-noted prior art, the searchfor new additives for fuels and lubricants continues. This continuingsearch has been prompted in part by the increasingly severe demands puton fuels and lubricants by efforts to reduce pollution caused byoperation of engines using such materials as well as economicconsiderations and material shortages. It is an object of the presentinvention to provide additives, processes, concentrates and compositionswhich satisfy these increased demands.

SUMMARY OF THE INVENTION

The condensation products of the present invention are made by theprocess comprising reacting

(A) at least one alpha haloalkyl hydroxy aromatic compound of thegeneral formula ##STR1## wherein Ar is a hydrocarbyl aromatic nucleus of6 to about 30 carbon atoms, or a substituted analog of such an aromaticnucleus substituted with one or more up to three each of lower alkoxy,lower alkylthio, chloro, or nitro substituents, each R is a nonfusedhydrocarbyl group of about 25 to about 700 carbon atoms, X is a halogenatom, each R' is independently a hydrogen atom, an alkyl group of 1 to36 carbon atoms, or a halogen-substituted alkyl group of 1 to about 36carbon atoms, n is 1 to 3 and m is 1 to 5 with the provisos that (i) thetotal number of carbon atoms in both the R' groups does not exceed 36and (ii) where m exceeds 1, one of the R groups can also be a ##STR2##with

(B) at least one alpha-beta olefinically unsaturated compound selectedfrom the group consisting of C₂₋₄₀ hydrocarbyl nitriles, C₂₋₄₀hydrocarbyl carboxylic acids and anhydrides, esters, amides and ammoniumand metal salts of said C₂₋₄₀ carboxylic acids,

the reaction of (A) with (B) resulting in the formation of acarbon-to-carbon bond, said bond including the carbon of at least one##STR3##

At least one hydroxy group of the hydroxy-aromatic compounds of FormulaI is directly bonded to an aromatic carbon of Ar. Preferably X is abromine or chlorine atom; and the haloalkyl group ##STR4## is a chloro-or bromomethyl group. If m exceeds 1, one R group can also be a ##STR5##

The nucleus Ar in Formula I can be purely hydrocarbyl in nature (e.g.,benzene, naphthene, toluene, xylene, etc.) or it can have one or more(up to a total of 3) optional substituents such as lower alkoxy (i.e.,of less than 7 carbon atoms, e.g., methoxy, 2-propyloxy, etc.)alkylthio, chloro or nitro substituents.

The aromatic compounds of the present invention have at least onenon-fused hydrocarbyl substituent (R in Formula I) which can besaturated or ethylenically unsaturated, aliphatic, alicyclic or aromaticin nature. The term "non-fused" in this application and the appendedclaims is used to indicate that the substituent is attached at only onecarbon to an aromatic ring of Ar. These R substituents are substantiallysaturated, (i.e., containing no more than one unsaturatedcarbon-to-carbon bond per every ten carbon-to-carbon single bonds) andare of about 25 and about 700 carbon atoms. Preferably they aresaturated alkyl groups. While free carbon of the aromatic nucleus Ar ofFormula I can bear a R substituent, it is preferable that no more thanthree do (i.e., m is 3). More typically, m is 1 or 2.

It is to be noted that when the term "hydrocarbyl" is used in describinga substituent in this specification and the appended claims, it is alsointended to embrace substantially hydrocarbyl substituents unlessexpressly stated otherwise. Such substantially hydrocarbyl substituentsare those which are substituted with non-hydrocarbyl groups which do notsubstantially affect the hydrocarbyl character or nature of thesubstituent in the context of the invention and which would, therefore,be considered to be within the scope of the term "hydrocarbyl" by askilled worker in the art. For example, it is obvious that a C₃₀hydrocarbyl substituent and a C₃₀ hydrocarbyl substituent substitutedwith a methyl mercapto or methoxy group would be substantially similarin their properties with regard to their use in this invention, andwould, in fact, be recognized as equivalents in the context of thisinvention by one of ordinary skill in the art.

Non-limiting examples of groups that do not significantly alter thehydrocarbyl nature of the hydrocarbyl substituents of this inventioninclude the following: Ether (especially hydrocarbyloxy and particularlypendant alkoxy groups of up to ten carbon atoms); Oxa, e.g., --O--linkages in the main hydrocarbyl chain; Hydroxy; Nitro; Cyano; Nonalphahalo, particularly fluoro-, chloro- and bromo-; Thioether (especiallypendant C₁ -C₁₀ alkyl thioethers); Thia, e.g., --S-- linkages in themain hydrocarbyl chain; Sulfonyl ##STR6## and Sulfinyl ##STR7##

In general, when non-hydrocarbyl groups are present in the Rsubstituents of Formula I, there will be no more than two such groupsfor every ten carbon atoms in the hydrocarbyl substituent; preferablynot more than one for each ten carbon atoms. Generally, however, it ispreferred that no such substituents be present and that the Rsubstituents be solely or purely hydrocarbyl in nature.

The non-fused hydrocarbyl substituents, R, of this invention aretypically long-chain, relatively high molecular weight hydrocarbylsubstituents having at least 25 carbon atoms, such as those typified bythe alkyl groups derived from petroleum wax, which is a predominantlystraight-chain aliphatic hydrocarbon of at least 25 carbon atoms.Relatively high molecular weight R groups derived from polymerization oflower olefins, particularly 1-monoolefins, can also be used as thesource of the hydrocarbyl substituent.

Generally, the sources of the hydrocarbyl R groups include principallythe high molecular weight substantially saturated petroleum fractionsand substantially saturated olefin polymers, particularly polymers ofmonoolefins having from 2 to about 30 carbon atoms. The especiallyuseful polymers are the polymers of 1-monoolefins such as ethylene,propene, 1-butene, isobutene, 1-hexene, 1-octene, 2-methyl-1-heptene,3-cyclohexyl-1-butene, and 2-methyl-5-propyl-1-hexene. Polymers ofmedial olefins, i.e., olefins in which the olefinic linkage is not atthe terminal position, likewise are useful. They are exemplified by2-butene, 3-pentene, and 4-octene.

Also useful are the interpolymers of the olefins such as those mentionedabove with other interpolymerizable olefinic substances such as aromaticolefins, cyclic olefins, and polyolefins. Such interpolymers include,for example, those prepared by polymerizing isobutene with styrene;isobutene with butadiene; propene with isoprene; ethylene withpiperylene; isobutene with chloroprene; isobutene with p-methyl styrene;1-hexene with 1,3-hexadiene; 1-octene with 1-hexene; 1-heptene with1-pentene; 3-methyl-1-butene with 1-octene; 3-3-dimethyl-1-pentene with1-hexene; isobutene with styrene and piperylene; etc.

The relative proportions of the monoolefins to the other monomers in theinterpolymers influence the stability and oil-solubility of the finalsubstituted hydroxy aromatic condensation products containing groupsderived from such interpolymers. Thus, for reasons of oil solubility andstability the R groups contemplated for use in this invention should besubstantially aliphatic and substantially saturated, i.e., they shouldcontain at least about 80%, preferably at least about 95%, on a weightbasis of units derived from the aliphatic monoolefins and no more thanabout 5% of olefinic linkages based on the total number ofcarbon-to-carbon covalent linkages. In most instances, the percentage ofolefinic linkages should be less than about 2% of the total number ofcarbon-to-carbon covalent linkages.

Specific examples of such interpolymers include copolymer of 95% (byweight) of isobutene with 5% of styrene; terpolymer of 98% of isobutenewith 1% of piperylene and 1% of chloroprene; terpolymer of 95% ofisobutene with 2% of 1-butene and 3% of 1-hexene; terpolymer of 60% ofisobutene with 20% of 1-pentene and 20% of 1-octene; copolymer of 80% of1-hexene and 20% of 1-heptene; terpolymer of 90% of isobutene with 2% ofcyclohexene and 8% of propene; and copolymer of 80% of ethylene and 20%of propene.

Another source of the substantially hydrocarbon R groups comprisessaturated aliphatic hydrocarbons such as highly refined high molecularweight white oils or synthetic alkanes such as are obtained byhydrogenation of high molecular weight olefin polymers illustrated aboveor high molecular weight olefinic substances.

The use of olefin polymers having number average molecular weights (Mn)of about 750-5000 is preferred. Higher molecular weight olefin polymershaving molecular weights as measured by vapor pressure osometry or gelpermeation chromatography from about 5000 to about 100,000 or higherhave been found to be useful in specific instances.

Examples of preferred R groups are those derived from polyisobutenes ofnumber average molecular weights ranging from about 400 to about 10,000.Preferably, these isobutenes have minimum Mn's of about 700 or about1000 and maximum Mn's of about 3000 or about 5000.

Such hydrocarbyl R groups can be bonded to the aromatic rings of the Armoiety of Formula I by techniques well known to those of skill in theart, such as alkylation reactions in the presence of Lewis acids such asBF₃, AlCl₃, SnCl₄, etc. Since such alkylation techniques are well known,they need not be described further at this point.

The alpha-haloalkyl hydroxy-aromatic compounds of this invention canoften be conveniently derived by methods discussed hereinafter fromhydrocarbyl-substituted hydroxyaromatic precursors of the generalformula; ##STR8## Typical of such precursors are the following:

2,4-di(polybutyl) phenol wherein each polybutyl group has an average of30 to 50 carbon atoms; 4-polypropyl phenol, the polypropyl group havingan Mn of about 450; and 4-polyisobutenyl phenol, the polyisobutyl grouphaving an Mn of about 2200, etc.

Many other suitable precursors within the above-discussed limitationswill readily come to the mind of the skilled artisan. Mixtures of two ormore of such precursors can also be used and in many instances may becommercially preferred because they do not involve costly separationprocesses in their production.

Further examples of hydroxy-aromatic precursors from which thealpha-haloalkyl compounds of this invention can be derived includesubstituted phenols, resorcinols, hydroquinones, catechols, anisoles,xylenols, hydroxydiphenyl compounds (i.e., phenyl phenols), benzylphenol, phenylethyl phenol, bisphenol-A, alpha and beta naphthol, alphaand beta methyl naphthol, ethoxy naphthol, methyl thio naphthol,anthracenol, phenylmethyl naphthol, phenanthrol, the monomethyl ether ofcatechol, phenoxy phenol, chlorophenol, and the like. Thus the Ar moietyof Formula I can be a phenyl, methylphenyl, diphenyl, naphthyl, anthryl,phenanthryl, chlorophenyl or phenoxyphenyl moiety.

The Ar moiety can also be a bridged moiety wherein two or more aromaticrings are connected through a bridging unit such as a covalentcarbon-to-carbon bond (i.e., directly linking the two aromatic rings);an oxygen, sulfur, polysulfide, ##STR9## methylene or substitutedmethylene groups (wherein the substitution is by C₁₋₇ hydrocarbylgroups), can also be used.

Particularly preferred hydroxy-aromatic precursors used as sources ofthe haloalkyl hydroxy-aromatic compounds of the present invention aremono-substituted phenols and naphthols, particularly themono-substituted phenols (i.e., where Ar is phenyl and n and m are bothone in Formula I). In such mono-substituted phenols, R can be arelatively high molecular weight long-chain group containing about 25 toabout 250 carbon atoms. Typical of such groups are alkyl and alkenylgroups made from homo- and interpolymers of ethylene, propylene,butylenes and isobutylene.

In view of the above limitations, it is clear that the alpha-halohydroxy-aromatic compounds of this invention will have a minimum ofabout 32 carbon atoms. The maximum number of carbon atoms is limitedonly by the size of the non-fused R substituent, i.e., 700 carbons.Preferably, the alpha-halo hydroxy-aromatic compounds will have aminimum of about thirty carbon atoms and a maximum of about 400 carbonatoms in the R portion of their molecules.

The alpha-haloalkyl hydroxy-aromatic compounds used in this inventioncan be made by a number of processes well known to those of the art. Aparticularly useful method is by reaction of a hydroxy-aromaticprecursor such as those described above in Formula II, with a carbonylreagent such as an aldehyde or ketone in the presence of a halogensource such as a hydrogen halide. In general, useful aldehydes orketones contain between one and about 36 carbon atoms. Carbonyl reagentscontaining one to ten carbon atoms and no carbon-to-carbon bondunsaturation are particularly preferred. To produce the desired##STR10## these aldehydes and ketones must be aliphatic or alicyclicalkyl in nature; preferably, they are aliphatic aldehydes such asformaldehyde, (and its polymers such as trioxane and paraformaldehyde aswell as solutions such as formalin), acetaldehyde, butanal, octanal,octadecanal, etc.

Thus, among the preferred aldehydes for use in making thealpha-halohydroxy alkyl-aromatic compounds of the present invention arethose of the general formula R'CHO, wherein R' is a hydrogen atom or analkyl group of up to 36 carbon atoms.

Preferred ketones which can be used to produce the desired ##STR11## arethose of the general formula ##STR12## wherein each R' group is an alkylgroup of up to 36 carbon atoms with the proviso that the total ofcarbons in both (R')s is about 36. Typical useful ketones includeacetone, methylethyl ketone, methylbutyl ketone, cyclohexanone, acetylcyclopentane, methyl octadecyl ketone, etc. Acetone and precursorsthereof (e.g., the diethyl ketal) are among the preferred ketones.

The halogen atom, X, is the afore-described ##STR13## can be a fluorine,chlorine, bromine or iodine atom but usually it is a chlorine or bromineatom. Typically, X is a chlorine atom.

Methods for reacting the above-described carbonyl reagents withhydroxy-aromatic precursors are well known to those skilled in the artand need not be discussed in detail here. Generally, about 0.5 to about5.0 moles, preferably about 1 to 2 moles, of carbonyl reagent per moleof hydroxy-aromatic precursor is reacted at a temperature of about -15°C. to about 300° C. in the presence of at least an equivalent amount ofat least one hydrogen halide. If desired the hydrogen halide can beomitted and introduced in a subsequent step. The reaction is oftencarried out in the presence of a non-volatile or volatile substantiallyinert organic liquid solvent or diluent (e.g., petroleum naphtha ordiluent mineral oil) for about 0.1 to about 48 hours. Preferred minimumreaction times are about one to about two hours while preferred maximumsare about ten to about eighteen hours. These reactions can be catalyzedby Lewis acids, particularly Lewis acid halides, such as BF₃, ZnCl₂,FeCl₃, etc.

Such reactions are disclosed in U.S. Pat. No. 2,964,442 which is herebyincorporated by reference for its relevant disclosures.

While the just-described carbonyl reagent/hydroxy-aromatic precursorreaction is among the preferred methods for producing thealpha-haloalkyl compounds of the present invention, it is by no meansthe only such method. Other methods such as free radical or ionichalogenation of an appropriately substituted hydroxy aromatic precursor(e.g., one having a methyl substituent) will readily occur to theskilled artisan. Therefore, in its broadest aspects, this invention isnot limited by the process used to produce the alpha-haloalkyl alkylatedhydroxy-aromatic compounds used in it.

The products of this invention are made by reacting the afore-describedalpha-haloalkyl alkylated hydroxy-aromatic compounds with at least onealpha-beta olefinically unsaturated compound selected from the groupconsisting of C₂₋₄₀ hydrocarbyl nitriles, C₂₋₄₀ hydrocarbyl carboxylicacids or derivatives thereof. The carboxylic acid derivativescontemplated include anhydrides, esters, amides, ammonium salts, metalsalts, etc., made by reacting the afore-said acids with various types ofmono- and polyamines, mono- or polyhydric alcohols, ammonia, metalsalts, etc., as described in further detail below.

The olefinic carboxylic acids used in preparing the compositions of thepresent invention may be either monobasic or polybasic in nature. Whenthey are polybasic, they are often dicarboxylic acids although tri- andtetracarboxylic acids can also be used. Generally, useful monobasicacids have three to about forty carbon atoms, while useful polybasicacids have four to forty carbon atoms. Preferably the maximum number ofcarbons for either type of acid is about twenty.

Exemplary monobasic olefinic carboxylic acids used in preparing theproducts of this invention are those of the formula: R°COOH wherein R°has between two and up to about 39, usually up to about 20 carbon atomsand is further characterized by the presence of at least oneolefinically unsaturated carbon-to-carbon bond within its structure. R°can be aliphatic or alicyclic in nature and can contain otherhydrocarboxyl substituents such as aryl groups, alkylaryl, heterocyclic,etc. Preferred acids correspond to the formula R"CH═CHCOOH or ##STR14##wherein R" is hydrogen or a saturated or ethylenically unsaturatedaliphatic substituent of up to about 37 carbon atoms. Usually R" ishydrogen or a C₁₋₇ alkyl group. While R° can contain more than oneolefinic linkage (either conjugated or nonconjugated), usually R°contains only one olefinic linkage.

Specific examples of useful α,β-olefinic monobasic carboxylic acids areacrylic acid, methacrylic acids, cinnamic acid, crotonic acid, 3-phenylpropenoic acid, α,β-decenoic acid, etc.

As stated above, the olefinic carboxylic acid reactant used to preparethe products of this invention can be polybasic, often dibasic,containing up to forty carbon atoms. Exemplary polybasic acids includemaleic acid, fumaric acid, mesaconic acid, itaconic acid and citraconicacid.

The olefinic nitriles used to prepare the products of the presentinvention are generally analogous to the aforedescribed acids in thatthey have structures in which at least one of the carboxylic acid grouphas been replaced by a nitrile group. They also contain about two toabout 40 carbon atoms exclusive of the nitrile carbons. Thus, suchcompounds as acrylonitrile, methylacrylonitrile, cinnamic nitrile,maleic and fumaric dinitrile, oleyl nitrile, 2-methylene glutaronitrile,etc., can be used to make the products of the present invention. Furtherexamples include 1-butylvinyl nitrile, 1-hexylvinyl nitrile,1-cyclohexenyl nitrile, 1-t-butylvinyl nitrile, 2-methylvinyl nitrile(i.e., crotonic nitrile), 2-dodecylvinyl nitrile, 2,2'-didodecylvinylnitrile, 2-cyclopentylvinyl nitrile, 2-octyl-2-methylvinyl nitrile, etc.Other useful nitriles include such compounds as 1-phenylvinyl nitrile,2-phenylvinyl nitrile, 1-tolylvinyl nitrile and 2-phenylethylvinylnitrile.

As noted before, the acid derivatives useful in preparing the productsof the present invention are generally anhydrides, esters, amides,amines, ammonium and metal salts of the afore-described acids. Methodsof preparing such derivatives are well known to those of skill in theart and they can be satisfactorily described by noting the reactantsused to produce them. Thus, for example, derivative esters for use inthe present invention can be made by esterifying monohydric orpolyhydric alcohols with any of the aforedescribed acids. In generalthese mono- and polyhydric alcohols contain from one to about thirtycarbon atoms, preferably, one to about twenty carbon atoms. Exemplaryaliphatic and alicyclic monohydric alcohols include methanol, ethanol,isopropanol, n-butanol, tertiary butanol, isooctanol, cyclopentanol,cyclohexanol, behenyl alcohol, hexacosanol, neopentyl alcohol, isobutylalcohol, benzyl alcohol, beta-phenylethyl alcohol, 2-methylcyclohexanol,beta-chloroethanol, monomethyl ether of ethylene glycol, monobutyl etherof ethylene glycol, monopropyl ether of diethylene glycol, monododecylether of triethylene glycol, monooleate of ethylene glycol, monostearateof diethylene glycol, secondary pentyl alcohol, tertiary butyl alcohol,5-bromo-dodec-5-enol, 3-nitro-octadecanol, the dioleate of glycerol,etc.

Useful polyhydric alcohols generally contain from two to ten hydroxygroups and two to about 25 carbons. These include, for example, ethyleneglycol, dipentylene glycol, triethylene glycol, tetraethylene glycol,dipropylene glycol, tripropylene glycol, dibutylene glycol, tributyleneglycol, neopentyl glycol and other alkylene glycols in which thealkylene radical contains from two to about eight carbon atoms. Otheruseful polyhydric alcohols include glycerol, monooleate of glycerol,monostearate of glycerol, monomethyl ether of glycerol, pentaerythritol,di- and tripentaerythritol, lower alkyl esters of 9,10-dihydroxy stearicacid, 1,2-butanediol, 2,3-hexanediol, trimethylolpropane,2,4-hexanediol, pinacol, erythritol, arabitol, sorbitol, mannitol,1,2-cyclohexanediol, xylene glycol, etc.

The derivative esters can also be derived from unsaturated alcohols suchas allyl alcohol, cinnamyl alcohol, propargyl alcohol,1-cyclohexene-3-ol, oleyl alcohol, etc. Still other classes of thealcohols capable of yielding the esters of this invention comprise theether-alcohols and amino-alcohols including, for example, theoxy-alkylene-, oxy-arylene-, amino-alkylene-, andamino-arylene-substituted alcohols having one or more oxy-alkylene,amino-alkylene or amino-arylene oxy-arylene radicals. They areexemplified by Cellosolve, Carbitol, phenoxyethanol,heptylphenyl-(oxypropylene)₆ -H, octyl-(oxyethylene)₃₀ -H,phenyl-(oxyoctylene)₂ -H, mono(heptylphenyl-oxypropylene)-substitutedglycerol, poly(styrene oxide), amino-ethanol, 3-amino ethyl-pentanol,di(hydroxyethyl)amine, p-aminophenol, tri(hydroxypropyl)amine,N-hydroxyethyl ethylene diamine, N,N,N',N'-tetrahydroxytrimethylenediamine, and the like. For the most part the ether-alcohols having up toabout 15 oxy-alkylene radicals in which the alkylene radical containsfrom one to about eight carbon atoms are preferred. Generally the mono-and polyhydric alkanols of up to about 16 carbon atoms and one to sixhydroxyl groups are preferred.

Similarly, amide and ammonium derivatives of the aforedescribed acidscan also be used to make the products of this invention. Suchderivatives are prepared from monoamino compounds, hydroxyaminocompounds, polyamino compounds, and hydroxy polyamine compounds. For thepurposes of this invention, hydrazines and organically substitutedhydrazines are included within the various classes of amino compounds.Mixtures of these various amino compounds containing two or more of theforegoing amines can also be employed to make useful nitrogenderivatives.

Among the amines useful in preparing the nitrogen derivatives for use inthis invention are monoamines. These monoamines can be tertiary, butmore typically they contain at least one H--N-- linkage. Thus primaryand secondary amines are typical. These amines are generally substitutedwith C₁₋₃₀ hydrocarbyl groups. Usually these hydrocarbyl substituentsare aliphatic in nature and contain between one and ten carbon atoms.Saturated aliphatic hydrocarbyl substituents containing one to tencarbon atoms are generally useful.

The hydrocarbyl substituents of the above-described monoamines can bealiphatic, cycloaliphatic, and aromatic substituents (includingaliphatic- and cycloaliphatic-substituted aromatic substituents andaromatic- and aliphatic-substituted cycloaliphatic substituents).

Among the preferred monoamines useful in making the derivatives used inmaking the products of the present invention are amines of the generalformula HNR² R³ wherein R² is an alkyl group of up to ten carbon atomsand R³ is a hydrogen atom or an alkyl group of up to ten carbon atoms.Another preferred class of monoamines are aromatic monoamines of thegeneral formula HNR⁴ R⁵ wherein R⁴ is a phenyl, alkylated phenyl,naphthyl or alkylted naphthyl group of up to ten carbon atoms and R⁵ isa hydrogen atom, an alkyl group of up to 10 carbon atoms or R⁴.Representative examples of these monoamines are ethyl amine, diethylamine, n-butyl amine, di-n-butyl amine, allyl amine, isobutyl amine,coco amine, stearyl amine, lauryl amine, methyl lauryl amine, oleylamine, aniline, paramethyl aniline, N-monomethyl aniline, diphenylamine, benzyl amine, tolyl amine, methyl-2-cyclohexyl amine, etc.

Hydroxy amines are also included in the class of useful monoamines. Suchcompounds are the hydroxy-hydrocarbyl-substituted analogs of theafore-described monoamines. Preferred hydroxy monoamines have thefollowing general formulae:

    HNR.sup.7 R.sup.6 and HNR.sup.9 R.sup.8

wherein R⁷ is an alkyl or hydroxy-substituted group of up to 10 carbonatoms, R⁶ is a hydrogen atom or R⁷, R⁹ is a hydroxy-substituted phenyl,alkylated phenyl, naphthyl or alkylated naphthyl of up to 10 carbonatoms and R⁸ is a hydrogen atom or R⁹ with provisos that at least one ofR⁷ and R⁶ and at least one of R⁹ and R⁸ is hydroxy-substituted.

Suitable hydroxy-substituted monoamines include ethanol amine,di-3-propanol amine, 4-hydroxybutyl amine, diethanol amine,n-methyl-2-propyl amine, 3-hydroxy aniline, N-hydroxyethyl-ethylenediamine, N,N-di(hydroxypropyl)propylene diamine, andtris(hydroxymethyl)methyl amine, etc. While, in general, those hydroxyamines containing only one hydroxy group will be employed as reactants,those containing more can also be used. Mixtures of two or more suchhydroxy amines can also be used.

Heterocyclic amines are also useful in making amide derivatives,providing they contain a primary or secondary amino group. The cycle canalso incorporate unsaturation and can be substituted with hydrocarbylsubstituents such as alkyl, alkenyl, aryl, alkaryl or aralkylsubstituents. In addition, the cycle can also contain other heteroatomssuch as oxygen and sulfur or other nitrogen atoms including those nothaving hydrogen atoms bonded to them. Generally, these cycles have 3 to10, preferably 5 to 6 ring members. Among such heterocycles areaziridines, azetidines, azolidines, tetra- and dihydropyridines,pyrroles, piperidines, imidazoles, indoles, di- andtetrahydro-imidazoles, piperazines, isoindoles, purines, morpholines,thiamorpholines, N-aminoalkyl morpholines, N-aminoalkyl thiamorpholines,azepines, azocines, azonines, azecines and tetra-, di- andperhydro-derivatives of each of the above, and mixtures of two or moreof these heterocycles. Preferred heterocyclic amines are the saturated5- and 6-membered heterocyclic amines, especially the piperidines,piperazines, and morpholines as discussed above.

Alkylene polyamines are also useful as amines for preparing nitrogenderivatives. These polyamines include hydroxy polyamines and usuallyconform, in most part, to the formula ##STR15## wherein a is an averageof integers between about 1 and about 10, preferably between 2 and 8;each A is independently a hydrogen atom, a hydrocarbyl group or ahydroxy-substituted hydrocarbyl group having up to about 10 atoms, and"Alkylene" is a divalent hydrocarbyl radical of one to eighteen carbons.Analogous polyamines wherein one or more ##STR16## moiety is replaced bya cyclic moiety such as a "(Alkylene)₂ N" moiety (e.g., piperazine) canalso be used. Usually A is a aliphatic group of up to about 10 carbonatoms or an aliphatic group of up to about 10 carbon atoms substitutedwith one or two hydroxy groups, and "Alkylene" is a lower alkylene grouphaving between 1 and 10, preferably 2 to 6 carbon atoms with the provisothat at least one A is hydrogen. Alkylene polyamines where each A ishydrogen with the ethylene polyamines are useful. Such alkylenepolyamines include ethylene polyamines, butylene polyamines, propylenepolyamines, pentylene polyamines, hexylene polyamines, heptylenepolyamines, etc. The higher homologs of such amines and relatedaminoalkyl-substituted piperazines are also included.

Polyamines useful in preparing the amide derivatives include ethylenediamine, triethylene tetramine, tris(2-aminoethyl)amine, propylenediamine, trimethylene diamine, hexamethylene diamine, decamethylenediamine, octamethylene diamine, di(heptamethylene)triamine, tripropylenetetramine, tetraethylene pentamine, trimethylene diamine, pentaethylenehexamine, di(trimethylene)triamine,2-heptyl-3-(2-aminopropyl)imidazoline, 1,3-bis(2-aminoethyl)imidazoline,1-(2-aminopropyl)piperazine, 1,4-bis(1-aminoethyl)piperazine,2-methyl-1-(2-aminobutyl)piperazine, etc. Higher homologs are obtainedby condensing two or more of the above-illustrated alkylene amines andlikewise are useful as are mixtures of two or more of theafore-described polyamines.

Ethylene polyamines, such as those mentioned above, are especiallyuseful for reasons of cost and effectiveness. Such polyamines aredescribed in detail under the heading "Diamines and Higher Amines" in"Kirk-Othmer Encyclopedia of Chemical Technology", Second Edition,Volume 7, pages 27-39, Interscience Publishers, Division of John Wileyand Sons, 1965. Such compounds are prepared most conveniently by thereaction of an alkylene chloride with ammonia or by reaction of anethylene imine with a ring-opening reagent such as ammonia, etc. Thesereactions result in the production of the somewhat complex mixtures ofalkylene polyamines, including cyclic condensation products such aspiperazines. These mixtures are particularly useful in preparing thecompositions of this invention. On the other hand, quite satisfactoryproducts can also be obtained by the use of pure alkylene polyamines.

Hydroxy polyamines, e.g., alkylene polyamines having one or morehydroxyalkyl substituents on the nitrogen atoms, are also useful inpreparing amide or ester derivatives. Preferred hydroxyalkyl-substitutedalkylene polyamines are those in which the hydroxyalkyl group is a lowerhydroxyalkyl group, i.e., having less than about 10 carbon atoms.Examples of such hydroxyalkyl-substituted polyamines includeN-(2-hydroxyethyl)ethylene diamine, N,N'-bis(2-hydroxyethyl)ethylenediamine, 1-(2-hyroxyethyl)piperazine, monohydroxypropyl-substituteddiethylene triamine, di-hydroxypropyl-substituted tetraethylenepentamine, N-(3-hydroxybutyl)tetramethylene diamine, etc.

Higher homologs are obtained by condensation of the above-illustratedhydroxyalkyl-substituted alkylene amines through amino radicals orthrough hydroxy radicals as well as mixtures of the above are likewiseuseful.

The amide derivatives useful in making the products of this inventioncan also be prepared from hydrazine or an organo-substituted hydrazineof the general formula ##STR17## wherein each R¹⁰ is independentlyhydrogen or a C₁ -C₃₀ hydrocarbyl substituent, usualy with at least oneR¹⁰ being a hydrogen atom. More generally at least two R¹⁰ groups arehydrogen. Often at least two R¹⁰ groups bonded to the same nitrogen atomare hydrogen and the remaining R¹⁰ groups are alkyl groups of up to tencarbon atoms.

Examples of substituted hydrazines ae methylhydrazine;N,N-dimethylhydrazine; N,N'-dimethylhydrazine; phenylhydrazine;N-phenyl-N'-ethylhydrazine; N-(p-tolyl)-N'-(n-butyl)hydrazine;N-(p-nitrophenyl)-N-methylhydrazine; N,N'-di-(p-chlorophenyl)hydrazine;N-phenyl-N'-cyclohexylhydrazine; etc.

Mixtures of two or more of the afore-described amines and polyamines canalso be used in making the nitrogen-containing derivatives used inmaking the products of this invention.

Also among the useful nitrogen-containing derivative products areN-acrylo- and methacrylo-amino sulfonic acids such as those disclosed inU.S. Pat. No. 3,717,687 which is hereby incorporated by reference forits relevant disclosures.

Means for the production of ester and nitrogen derivatives from theafore-described alcohols and amines are well known to those of skill inthe art and need not be described in detail here.

The ammonium salt derivatives can also be made from any of theafore-described amines as well as from tertiary amino analogs of them(i.e., analogs wherein the --NH groups have been replaced with--N-hydrocarbyl or --N-hydroxy hydrocarbyl groups), ammonia or ammoniumcompounds (e.g., NH₄ Cl, NH₄ OH, etc.) by techniques well known to thoseof skill in the art.

The metal salt derivatives useful in making the products of the presentinvention can also be made by techniques well known to those of skill inthe art. Preferably they are made from a metal, mixture of metals, metalsalt or mixture of metal salts where the metal is chosen from Group Ia,Ib, IIa, or IIb of the periodic table although metals from Groups IVa,IVb, Va, Vb, VIa, VIb, VIIb and VIII can also be used. The gegan ion ofthe metal salt can be inorganic such as halide, sulfide, oxide,hydroxide, nitrate, sulfate, thiosulfate, phosphite, phosphate, etc., ororganic such as lower alkanoic, sulfonate, etc. The salts formed fromthese metals and the acid products can be either "normal" salts whereinthe metal and acid are present in stoichiometric amounts or "overbased"salts. The production of the latter are well known to those of skill inthe art and are described in detail in the afore-cited "LubricantAdditives" by M. W. Ranney, pages 67-77, which is hereby incorporated byreference for its relevant disclosures.

To form the products of this invention, the afore-described haloalkylhydroxy-aromatic compounds and carboxylic acid, acid derivative ornitrile compounds are reacted together at a temperature ranging fromabout 15° C. to the decomposition temperature of the reactant or productpresent having the lowest decomposition temperature. Preferably thelowest reaction temperature is about 100° C., more preferably 150° C.,while the highest reaction temperature is preferably about 300° C., morepreferably 250° C. Generally the ratio of hydroxy compound to acid, acidderivative, or nitrile lies between about 0.5:1 to about 2:1. Thereaction is normally carried out in about 0.5 to about 96 hours. It isoften desirable to carry out such reactions in the presence of an inertsolvent-diluent such as a hydrocarbon or ether boiling from about 50° C.to 200° C. or lubricant base stocks such as those described below.

After reaction the acidic or nitrile groups in the products of thisinvention can be further modified by post-treatment with one of theafore-described alcohols, amino compounds, metals or salts. Suchreactions and the means and conditions for carrying them out are wellknown to those of skill in the art.

Post-treated reaction products can be made by reacting the reactionproducts described hereinabove with a post-treating reactant selectedfrom the group consisting of (1) mono- and polyhydric alkanols andalkenols of 1 to about 10 carbon atoms and 1 to about 6 hydroxyl groups,(2) monoepoxides of C₂₋₁₈ alkenes, (3) alkyl mono amines of 1 to about18 carbon atoms, (4) alkylene polyamines of 2 to about 10 nitrogen atomsand 2 to about 36 carbon atoms and (5) mixtures of two or more of (1) to(4) including mixtures within one class and mixtures of species selectedfrom two or more classes.

A nitrile group can be converted to an amidine or amide through reactionwith an amine, etc. or to an amino group through hydrogenation.

The condensation and reaction products of this invention arecharacterized by the fact that the reaction of the hydroxyaromaticcompound (A) with the olefinic acid or nitrile (B) results in theformation of carbon-to-carbon bond which includes as one of its carbonatoms the carbon bearing the X atom in at least one ##STR18## This meansthat the reaction of (A) with (B) is not a simple esterificationalthough some minor amount of esterification may occur. The other carbonof the newly formed carbon-to-carbon bond is believed to come from theacid or nitrile compounds (B).

The following non-limiting examples demonstrate the practice of thepresent invention in its various aspects. All parts and percentages areby weight unless expressly stated otherwise.

EXAMPLE 1(a)

A mixture of 1412 parts of phenol and 1090 parts of benzene is heated to50°-55° C.; then 283 parts of a boron trifluoride phenol complex (BF₃ ·2Phenol) is added over twenty minutes. Following this addition, 5000parts of a polyisobutene having a Mn of about 1000 is added. The mixtureis stirred for two hours at 55°-60° C. and then 645 parts of ammoniumhydroxide is added. Stirring is continued for an additional hour. Themixture is heated to 160° C. for four hours while an azeotrope ofphenol, water and benzene distills from it. Stripping the mixture to220° C./10 mm Hg and filtering it through diatomaceous earth providesthe desired alkylated phenol which has a Mn of 1047 and an infraredspectrum consistent with its structure as an alkylated phenol.

EXAMPLE 1(b)

A mixture of 4549 parts of the alkylated phenol described in Example1(a), 540 parts of paraformaldehyde and 2500 parts of petroleum naphthaboiling between 96° and 102° C. is heated to 55°-60° C. for two hours toaffect homogenization. Gaseous hydrogen chloride is then bubbled intothe reaction mixture at a rate of 2 cfh through a glass tube whoseorifice is located below the mixture's surface for a total of twelvehours. The mixture is stirred for an additional 3.5 hours and blown withnitrogen at a rate of 1.5 to 2 cfh for an additional eight hours. Themixture is filtered through filter aid and the filtrate stripped to 90°C./25 mm Hg to provide the final product which has a chlorine content of2.1%, and an infrared spectrum consistent with its structure as achloromethylated alkylated phenol.

EXAMPLE 1(c)

A mixture of 4302 parts of the chloromethyl alkylated phenol describedin Example 1(b) and 274 parts of maleic anhydride is heated to 210°-215°C. for 7.5 hours while being nitrogen blown. Excess maleic anhydride isremoved by stripping the mixture to 210° C./10 mm and the reactionmixture diluted with 2973 parts of a diluent oil. Filtration with filteraid provides a 40% solution of the desired product.

EXAMPLE 2

To 2028 parts of the 40% oil solution described in Example 1(c) at140°-145° C. is slowly added 65 parts of a polyethylene polyamine havingan average of three to seven amino groups per molecule. The reactionmixture is heated at 175°-180° C. for two hours and the mixture thenfiltered through diatomaceous earth to provide a 40% oil solution of thedesired product.

Examples 3-7 are all carried out in substantially the same fashion usingthe following procedure: A mixture of haloalkyl substituted phenol andunsaturated compound is heated under nitrogen to a temperature of200°-240° C. for four to six hours. The mixture is stripped toapproximately 200° C./10-25 mm Hg to obtain a residue which is thendiluted with an approximately equal volume of diluent oil and filteredthrough diatomaceous earth to yield a filtrate which is a solution ofthe desired product. Details as to the reactants and proportions used inExamples 3 to 7 are summarized in Table I.

                  TABLE I                                                         ______________________________________                                        Ex.                                                                           No.  α-Haloalkylphenol (moles)                                                                Unsaturated Reactant (moles)                            ______________________________________                                        3    Example 1(b)  (0.245)                                                                          2-Ethylhexyl acrylate(0.25)                             4    Example 1(b)  (0.245)                                                                          di(n-butyl)fumarate  (0.25)                             5    Example 1(b)  (0.32)                                                                           Itaconic Acid  (0.32)                                   6    Example 1(b)  (0.2)                                                                            4-Cyclohexene-1,2-  (0.2)                                                     dicarboxylic acid                                                             anhydride                                               7    Alkyl-substituted (2.55)                                                                       Maleic Anhydride  (2.8)                                      chloromethyl                                                                  phenol.sup.1                                                             ______________________________________                                         .sup.1 Made alkylating phenol with a mixture of C.sub.15-18 1Olefins          according to general procedure described in Example 1(a).                

EXAMPLE 8(a)

A mixture of 1030 parts of the alkylated phenol described in Example1(a), 40 parts sodium hydroxide and 370 parts Stoddard solvent isrefluxed under nitrogen at 128°-168° C. for 1.75 hours as waterazeotropes out as a distillate. An additional charge of 180 parts ofStoddard solvent is added and refluxing continued for another hour untilvirtually all the water is removed as an azeotrope. Then at 155°-162° C.51.5 parts of sulfur dichloride is added dropwise to the reactionmixture over 1.5 hours and the mixture heated at 162° C. for 2.5 hours.After being cooled to room temperature, the reaction mixture is treatedwith 50 parts of water and 10 parts of concentrated hydrochloric acid.It is then refluxed at 106°-156° C. for 5.0 hours under nitrogen. Wateragain azeotropes out of the mixture. Twenty parts of diatomaceous earthis added to the reaction mixture and it is filtered at 70° C. Thefiltrate is stripped to 152° C./13 mm Hg to provide the desiredsulfurized phenol product, which has a sulfur content of 1.64% and a Mnof 1207 (by vapor pressure osometry).

EXAMPLE 8(b)

A mixture of 809 parts of the sulfurized phenol described in 8(a) and575 parts of hydrocarbon diluent boiling at 96° C. to 102° C. is treatedat 46°-49° C. with a stream of gaseous hydrogen chloride for 0.5 hour.Then 38 parts of paraformaldehyde is slowly added while HCl treatmentcontinues. The mixture is kept at 48°-51° C. for 6 hours while HCltreatment continues and a total of 69 parts of gaseous hydrogen chlorideis added to the reaction mixture. The mixture is heated to 81°-105° C.for four hours while water azeotropes from it. Fifteen parts ofdiatomaceous earth is added and the mixture filtered. The filtrate isstripped to 115° C./23 mm Hg to provide the desired final product whichhas a sulfur content of 1.59% and a chlorine content of 1.28%.

EXAMPLE 8(c)

A mixture of 767 parts of the chloromethylated sulfurized phenoldescribed in 8(b) and 30 parts of maleic anhydride is heated at208°-211° C. for 5 hours. Then 523 parts of diluent mineral oil isadded. The mixture is stripped to 219° C./20 mm Hg and filtered throughdiatomaceous earth to provide as a filtrate a solution of the desiredproduct containing 40% mineral oil.

EXAMPLE 9

To 500 parts of the product described in Example 8(c) at 110° C. undernitrogen is added 10.5 parts of the polyamine described in Example 2.The mixture is heated at 156° C. for 3.5 hours. Stripping to 180° C./21mm and filtration through diatomaceous earth provides an oil solution ofthe final product. This solution has a nitrogen content of 0.71%.

EXAMPLE 10

A mixture of 1504 parts of the reaction product of Example 8(c) and 45parts of pentaerythritol is heated under nitrogen blowing at 205°-211°C. for 12 hours. Then 27 parts of diluent oil is added to the mixtureand it is filtered through diatomaceous earth to provide an oil solutionof the desired product.

EXAMPLE 11(a)

A mixture of 3400 parts of the product of Example 1(c) and 17 parts ofwater is heated to 90°-100° C. for 2.5 hours. An infrared spectrum ofthe product shows a substantial reduction in anhydride absorptions, thusdemonstrating the substantial presence of the desired free diacid.

EXAMPLE 11(b)

To a mixture of 2982 parts of the product described in Example 11(a) and24 parts of lithium hydroxide monohydrate catalyst at 90° C. is added 86parts of propylene oxide. Provision is made for recycling the propyleneoxide as it evaporates from the reaction mixture. The mixture is kept at90°-100° C. for four hours while an additional 105 parts of propyleneoxide is fed into it. The reaction temperature is then raised in stagesto 180°-190° C. An additional 2.4 grams of lithium hydroxide monohydratecatalyst is added and the reaction mixture heated for ten hours at150°-160° C. Stripping of the mixture to 160° C./4 mm Hg followed byaddition of 95 parts of a diluent oil and filtration throughdiatomaceous earth provides the desired product as a 60% solution indiluent oil.

EXAMPLE 12

A mixture of 2945 parts of 60% solution in diluent oil of the reactionproduct described in Example 1(c) and 172 parts pentaerythritol isheated to 200°-210° C. for five hours. The reaction mixture is thencooled to 165° C. and 27 parts of the polyamine described in Example 2is added. The mixture is heated to 160°-165° C. for three hours. Diluentoil (123 parts) and filter aid are added to the reaction mixture and itis filtered to provide a 60% active oil solution of the desired product.This solution has a nitrogen content of 0.28%.

EXAMPLE 13

A mixture of 1000 parts of the chloromethylated phenol described in 1(b)and 120 parts of 2-methylene glutaronitrile is heated at 210°-250° C.for a total of seven hours. Provision is made for collection of the HClevolved in a caustic trap and at the end of the reaction substantiallyall of the theoretical amount of HCl has been released. The mixture isthen cooled and 110 parts of diluent oil is added. This mixture isfiltered through diatomaceous earth to provide a solution of the desiredproduct.

EXAMPLE 14

A mixture of 100 parts of the oil solution described in Example 13 and15 parts of a commercial polyethylene polyamine having a nitrogencontent of 33.8% and an average composition corresponding topentaethylene hexamine is slowly stirred at 90° C. as a total of 1.4parts of gaseous hydrogen sulfide catalyst is slowly introduced into it.The reaction mixture is heated at 140°-150° C. under nitrogen for ninehours. The reaction mass is then filtered through filter aid at 100° C.to provide an oil solution of the desired product, which ischaracterized by its infrared spectrum having absorptions atapproximately 3.12 microns indicative of ##STR19## groups.

As previously indicated, the condensation products of this invention areuseful as additives in preparing lubricant compositions where theyfunction primarily as detergents and dispersants, particularly where theoil is subjected to high temperature environments or to cyclic stressessuch as those encountered in stop-and-go automobile driving. Many suchcompositions are particularly useful in dispersing engine sludge andreducing engine varnish. The products of this invention can be employedin a variety of lubricant compositions based on diverse oils oflubricating viscosity, including natural and synthetic lubricating oilsand mixtures thereof. These lubricant compositions include crankcaselubricating oils for spark-ignited and compression-ignited internalcombustion engines, including automobile and truck engines, two-cycleengines, rotary engines, aviation piston engines, marine and railroaddiesel engines, and the like. In addition, automatic transmissionfluids, transaxle lubricants, gear lubricants, metal-working lubricants,hydraulic fluids and other lubricating oil and grease compositions canalso benefit from the incorporation therein of the products of thepresent invention.

Natural oils useful in making these compositions include animal oils andvegetable oils (e.g., castor oil, lard oil) as well as liquid petroleumoils and solvent-refined or acid-refined mineral lubricating oils of theparaffinic, naphthenic or mixed paraffinic-naphthenic types. Oils oflubricating viscosity derived from coal or shale are also useful baseoils. Synthetic lubricating oils include hydrocarbon oils andhalosubstituted hydrocarbon oils such as polymerized andinterpolymerized olefins (e.g., polybutylenes, polypropylenes,propylene-isobutylene copolymers, chlorinated polybutylenes, etc.);alkylbenzenes (e.g., dodecylbenzenes, tetradecylbenzenes,dinonylbenzenes, di-(2-ethylhexyl)-benzenes, etc.); polyphenyls (e.g.,biphenyls, terphenyls, etc.); and the like.

Alkylene oxide polymers and interpolymers and derivatives thereof wherethe terminal hydroxyl groups have been modified by esterification,etherification, etc. constitute another class of known syntheticlubricating oils. These are exemplified by the oils prepared throughpolymerization of ethylene oxide or propylene oxide, the alkyl and arylethers of these polyoxyalkylene polymers (e.g., methyl-polyisopropyleneglycol ether having an average molecular weight of 1000, diphenyl etherof polyethylene glycol having a molecular weight of 500-1000, diethylether of polypropylene glycol having a molecular weight of 1000-1500,etc.) or mono- and polycarboxylic esters thereof, for example, theacetic acid esters, mixed C₃ -C₈ fatty acid esters, or the C₁₃ Oxo aciddiester of tetraethylene glycol.

Another suitable class of synthetic lubricating oils comprises theesters of dicarboxylic acids (e.g., phthalic acid, succinic acid, maleicacid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipicacid, linoleic acid dimer, etc.) with a variety of alcohols (e.g., butylalcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethyleneglycol, etc.). Specific examples of these esters include dibutyladipate, di(2-ethylhexyl)sebacate, di-n-hexyl fumarate, dioctylsebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate,didecyl phthalate, dieicosyl sebacate, the 2-ethylhexyl diester oflinoleic acid dimer, the complex ester formed by reacting one mole ofsebacic acid with two moles of tetraethylene glycol and two moles of2-ethylhexanoic acid and the like.

Esters useful as synthetic oils also include those made from C₅ to C₁₂monocarboxylic acids and polyols and polyol ethers such astrimethylolpropane, pentaerythritol, dipentaerythritol, etc.

Silicon-based oils such as the polyalkyl-, polyaryl-, polyalkoxy-, orpolyaryloxy-siloxane oils and silicate oils comprise another usefulclass of synthetic lubricants (e.g, tetraethyl silicate, tetraisopropylsilicate, tetra-(2-ethylhexyl)silicate,tetra-(4-methyl-2-tetraethyl)silicate,tetra-(p-tert-butylphenyl)silicate,hexyl-(4-methyl-2-pentoxy)disiloxane, poly(methyl)siloxanes,poly(methylphenyl)siloxanes, etc.). Other synthetic lubricating oilsinclude liquid esters of phosphorus-containing acids (e.g., tricresylphosphate, trioctyl phosphate, diethyl ester of decane phosphonic acid,etc.), polymeric tetrahydrofurans and the like.

The preferred lubricating oils which serve as base stocks for thelubricant compositions of this invention have viscosities ranging fromabout 100 centistokes at 0° F. to about 2000 centistokes at 210° F.

Generally, the lubricant compositions of the present invention containan amount of the products of this invention sufficient to provide thecomposition with sludge dispersancy and engine detergent properties.Normally this amount will be about 0.05 to about 20, preferably about0.50 to about 10% of the total weight of the lubricant composition. Inlubricating oils operated under extremely adverse conditions, such aslubricating oils for marine diesel engines, the reaction products ofthis invention may be present in amounts of up to about 30% by weight.

The normally liquid fuel compositions of this invention are generallyderived from petroleum sources though they may include those producedsynthetically by the Fischer-Tropsch and related processes, theprocessing of organic waste material or the processing of coal, ligniteor shale rock. Such fuel compositions have varying boiling ranges,viscosities, cloud and pour points, etc., according to their end use asis well known to those of skill in the art. Among such fuels are thosecommonly known as motor and aviation gasoline, diesel fuels, jet enginefuel, kerosene, distillate fuels, heating oils, residual fuels, bunkerfuels, etc. The properties of such fuels are well known to skilledartisans as illustrated, for example, by ASTM Specifications D #396-73(Fuel Oils) and D #439-73 (Gasolines) available from the AmericanSociety for Testing Materials, 1916 Race Street, Philadelphia, Pa.19103.

The fuel compositions of the present invention can contain about 0.001%to about 5% (based on the weight of the final composition), preferablyabout 0.001% to about 1%, of the above-described products. The presenceof these products can impart many desirable characteristics to the fuelcomposition depending upon the particular composition and fuel mixtureselected. Thus in gasolines they may improve the overall compositionability to retard corrosion of metal parts with which it may come incontact or improve the fuel's ability to clean carburetors and reducecarburetor icing. On the other hand, these products can be used in fueloil compositions and other normally liquid petroleum distillate fuelcompositions to impart anti-screen clogging and demulsifying propertiesto the fuel.

The fuel compositions of this invention can contain, in addition to theproducts of this invention, other additives which are well known tothose of skill in the art. These can include anti-knock agents such astetraalkyl lead compounds, lead scavengers such as haloalkanes, depositpreventers or modifiers such as triaryl phosphates, dyes, cetaneimprovers, anti-oxidants such as 2,6-di-tertiary-butyl-4-methylphenol,rust inhibitors, such as alkylated succinic acids and anhydrides,bacteriostatic agents, gum inhibitors, metal deactivators, uppercylinder lubricants and the like.

The lubricant compositions of the present invention can contain, inaddition to the products of this invention, other additives that arenormally used in lubricants. Such additives include, for example,auxiliary detergents of the ash-forming and of the ashless type,viscosity index improving agents, pour-point depressants, anti-foamagents, extreme pressure agents, rust-inhibiting agents, oxidation- andcorrosion-inhibiting agents.

In one embodiment of the present invention, the afore-described productsare combined with other ashless dispersants for use in fuels andlubricants. Such ashless dispersants are preferably esters of a mono- orpolyol and a high molecular weight mono- or polycarboxylic acidacylating agent containing at least 30 carbon atoms in the acyl moiety.Such esters are well known to those of skill in the art. See, forexample, French patent No. 1,396,645; British patents Nos. 981,850 and1,055,337; and U.S. Pat. Nos. 3,255,108; 3,311,558; 3,331,776;3,346,354; 3,579,450; 3,542,680; 3,381,022; 3,639,242; 3,697,428;3,708,522; and, British Patent Specification No. 1,306,529. Thesepatents are expressly incorporated herein by reference for theirdisclosure of suitable esters and methods for their preparation.

Generally, the weight ratio of the reaction products of this inventionto the aforesaid ashless dispersants is about 0.1 to 10.0, preferablyabout 1.0 to 10 parts of reaction product to 1 part ashless dispersant.Preferred weight ratios are between 0.5 to 2.0 parts reaction product to1 part dispersant. In still another embodiment of this invention, theinventive additives are combined with Mannich condensation productsformed from substituted phenols, aldehydes, polyamines, and substitutedpyridines. Such condensation products are described in U.S. Pat. Nos.3,649,659; 3,558,743; 3,539,633; 3,704,308; and 3,725,277, which areincorporated herein by reference for their disclosure of the preparationof the Mannich condensation products and their use in fuels andlubricants. When the additives of this invention are combined with theMannich condensation products, a weight ratio of about 10 to about 0.1parts reaction product of this invention per 1 part Mannich condensationproduct is used.

The products of this invention can be added directly to the fuel orlubricant to be treated or they can be diluted with an inertsolvent/diluent such as the various oils and normally liquid fuelsdescribed in detail above to form an additive concentrate. Theseconcentrates generally contain about 20 to about 90 percent product andcan contain in addition any of the above-described prior art additives,particularly the afore-described ashless dispersants in the aforesaidproportions.

The fuel compositions of this invention are exemplified by thefollowing.

EXAMPLE 15

A gasoline having a Reid vapor pressure of 8.4 psi and containing 120parts per million parts of gasoline of the reaction product described inExample 2.

EXAMPLE 16

A diesel fuel oil containing 250 parts per million parts of fuel of thereaction product described in Example 4.

EXAMPLE 17

A gasoline having a Reid vapor pressure of 12 psi and containing 2.3grams per gallon of tetraethyl lead and 75 parts per million parts ofgasoline of the reaction product of Example 12.

Lubricant compositions and concentrate formulation of the presentinvention are exemplified by the following.

EXAMPLE 18

A solvent-refined, neutral SAE 10 mineral oil containing 0.5% of thereaction product described in Example 2.

EXAMPLE 19

A synthetic lubricant comprised predominantly of C₅ -C₉ normal alcoholesters of a 50/50 molar mixture of adipic and glutaric acids containing0.5% of the reaction product described in Example 4.

EXAMPLE 20

A concentrate for use in blending gasolines comprised of 50% of themineral oil of Example 18 and 50% of the product described in Example 4.

The solvent/diluents used in the additive concentrates of this inventionare generally substantially inert, normally liquid organic materialssuch as hydrocarbon solvents (e.g., benzene, heptane, cyclohexane, mixedxylenes, petroleum naphthas and reformates, etc.), various petroleumfuel oil mixtures, lubricating oils and mixtures of same and the like.

As used in the specification and the appended claims, the term"substantially inert" when used to refer to solvents, diluents,concentrate base stocks and the like, is intended to mean that thesolvent, diluent, etc., is inert to chemical or physical change underthe conditions in which it is used so as not to materially interfere inan adverse manner with the preparation, storage, blending and/orfunctioning of the compositions, additive, compound, etc., of thisinvention in the context of its intended use. For example, small amountsof a solvent, diluent, etc., can undergo minimal reaction or degradationwithout preventing the making and using of the invention as describedherein. In other words, such reaction or degradation, while technicallydiscernible, would not be sufficient to deter the practical worker ofordinary skill in the art from making and using the invention for itsintended purposes. "Substantially inert" as used herein is, thus,readily understood and appreciated by those of ordinary skill in theart.

The lubricant and liquid fuel compositions of this invention and thereaction products and the processes for preparing those products havebeen specifically set forth above to aid those skilled in the art inunderstanding and practicing the invention. Many obvious variations anddepartures from the specific disclosure will be apparent to those ofskill in the art based on principles and teachings herein and in theprior art. Such variations and departures are contemplated as beingwithin the scope of the present invention as defined by the appendedclaims.

What is claimed is:
 1. A lubricant composition comprising a major amountof at least one lubricating oil and a minor, but engine sludgedispersing, amount of a product made by the process comprising reactingat a temperature ranging from about 100° C. to about 300° C.(A) at leastone alpha haloalkyl hydroxy aromatic compound of the general formula##STR20## wherein Ar is a hydrocarbyl aromatic nucleus of 6 to about 30carbon atoms, said aromatic nucleus substituted with one or more up to 3each of lower alkoxy, lower alkylthio, chloro, or nitro substituents,each R is a nonfused hydrocarbyl group of about 25 to about 700 carbonatoms, X is a halogen atom, each R' is independently a hydrogen atom, analkyl group of 1 to 36 carbon atoms, or a halogen-substituted alkylgroup of 1 to about 36 carbon atoms, n is 1 to 3 and m is 1 to 5 withthe provisos that (i) the total number of carbon atoms in both the R'groups does not exceed 36 and (ii) where m exceeds 1, one of the Rgroups can also be a ##STR21## with (B) at least one alpha-betaolefinically unsaturated compound selected from the group consisting ofC₂₋₄₀ hydrocarbyl nitriles, and ammonium and metal salts of said C₂₋₄₀carboxylic acids; the ratio of (A) to (B) is between about 0.5:1 toabout 2:1, and the reaction of (A) with (B) resulting in the formationof a carbon-to-carbon bond, said bond including the carbon of at leastone ##STR22##
 2. A composition as claimed in claim 1 wherein m is 1 or2.
 3. A composition as claimed in claim 2 wherein each R is a homo- orinterpolymer of ethylene, propylene, butylene or isobutylene.
 4. Acomposition as claimed in claim 2 wherein both R' groups are hydrogenatoms and X is a chlorine atom.
 5. The composition of claim 3 wherein Aris a benzene nucleus and the reaction temperature is between about 150°and about 250° C.
 6. The composition of claim 5 wherein one or more ofthe R groups are derived from polyisobutene having number averagemolecular weight Mn ranging from about 400 to about 10,000.
 7. Thecomposition of claim 6 wherein both R' are hydrogen atoms and (B) is anolefinic nitrile selected from the group consisting of acrylonitrile,methacrylonitrile, cinnamic nitrile, oleyl nitrile, 2-methyleneglutaronitrile, 1-butylvinyl nitrile, and crotonic nitrile.
 8. Thecomposition of claim 7 wherein the R groups are derived frompolyisobutylene having number average molecular weight Mn ranging fromabout 1000 to about
 3000. 9. The composition of claim 8 wherein (B) isselected from acrylonitrile, oleyl nitrile and2-methylene-glutaronitrile.
 10. The composition of claim 9 wherein thereaction is carried out in the presence of a normally liquid inertsolvent or diluent.
 11. The composition of claim 4 wherein Ar is abenzene nucleus and (B) is a metal salt of C₂₋₄₀ carboxylic acids, withsaid metal being selected from Groups Ia, Ib, IIa, or IIb of thePeriodic Table.
 12. The composition of claim 11 wherein one or more ofthe R groups are derived from polyisobutene having number averagemolecular weight Mn ranging from about 400 to about 10,000.
 13. Thecomposition of claim 12 wherein the reaction temperature is betweenabout 150° and about 250° C.
 14. The composition of claim 13 wherein thereaction is carried out in the presence of a normally liquid inertsolvent or diluent.
 15. The composition of claim 4 wherein Ar is abenzene nucleus and (B) is an ammonium salt of C₂₋₄₀ carboxylic acids,said salt being prepared from the corresponding amino compounds.
 16. Thecomposition of claim 15 wherein one or more of the R groups are derivedfrom polyisobutylene having number average molecular weight Mn rangingfrom about 700 to about 5000.